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• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
  • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
  • C07C29/03—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2
  • C07C29/04—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2 by hydration of carbon-to-carbon double bonds
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
  • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
  • B01J27/053—Sulfates
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/08—Heat treatment
  • B01J37/082—Decomposition and pyrolysis
  • B01J37/084—Decomposition of carbon-containing compounds into carbon
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B32/00—Carbon; Compounds thereof
  • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
  • C07B61/00—Other general methods
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
  • C07C41/01—Preparation of ethers
  • C07C41/05—Preparation of ethers by addition of compounds to unsaturated compounds
  • C07C41/06—Preparation of ethers by addition of compounds to unsaturated compounds by addition of organic compounds only
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C67/00—Preparation of carboxylic acid esters
  • C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
  • C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
  • C07C69/533—Monocarboxylic acid esters having only one carbon-to-carbon double bond
  • C07C69/54—Acrylic acid esters; Methacrylic acid esters
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
  • B01J21/18—Carbon
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
  • B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
  • B01J31/08—Ion-exchange resins
  • B01J31/10—Ion-exchange resins sulfonated

Definitions

• the present invention relates to a sulfonic acid group-containing carbonaceous material produced by carbonization and sulfonation of an organic substance (hereinafter referred to as "carbon-based solid acid”), a catalyst comprising the solid acid, and methods for various reactions such as hydration of olefins using the solid acid as catalyst.
• carbon-based solid acid an organic substance
• catalyst comprising the solid acid
• Solid acids are useful for various purposes and, particularly, promising in use as catalyst for various reactions in an industrial process because the process can be simplified, and various types of solid acids have been developed therefore.
• a typical one of such solid acids is ion-exchange resin which is a polymer having sulfonic acid group.
• the ion-exchange resin has limited uses or using conditions due to defects such as low thermal stability.
• Nafion or the like that is a high heat-resistance resin has been also developed, but it is too expensive to be used for industrial purposes.
• carbon-based solid acids which can be obtained by carbonization and sulfonation of an aromatic compound or saccharide have been developed.
• Non-Patent Document 1 Non-Patent Document 2, Non-Patent Document 3, Patent Document 1, and Patent Document 2.
• the solid acids are useful also as catalyst for hydration of olefins.
• the hydration reaction of olefins is a reaction important for production of alcohols, ketones or the like, and industrially utilized.
• Isopropyl alcohol, 2-butanol, and methyl ethyl ketone are produced by various methods using hydration of propylene or n-butene (Non-Patent Document 4 and Non-Patent Document 5).
• a method using sulfuric acid is mainly adapted in plants in the world.
• Non-Patent Document 6 With respect to the hydration reaction of olefins, only an example in which hydration reaction of 2,3-dimethyl-2-butene is carried out at low temperature (70°C) using such a carbon-based solid acid as catalyst is disclosed without concrete disclosure or suggestion of a catalyst, a reaction condition and the like which are industrially practicable in application to other olefins (Non-Patent Document 6).
• the solid acids mentioned above are recognized to have a problem in the resistance of the acid radical possessed thereby.
• the present invention has an object to provide a carbon-based solid acid which has high activity and high thermal stability and is useful as catalyst for various reactions such as hydration of olefins.
• a first aspect of the invention relates to a carbon-based solid acid obtained by carbonization and sulfonation of an organic substance, and having a reduction rate of 10 mol% or less of acid content caused by immersing the solid acid in hot water of 120°C for 2 hours.
• a second aspect of the invention relates to a carbon-based solid acid wherein the organic substance in the first aspect of the invention comprises a saccharide having ⁇ 1-4 glycoside bond.
• a third aspect of the invention relates to a carbon-based solid acid wherein the organic substance in the first aspect of the invention comprises cellulose or lignin.
• a fourth aspect of the invention relates to a carbon-based solid acid wherein the organic substance in the first aspect of the invention comprises amylase as a main component.
• a fifth aspect of the invention relates to a method for producing an olefin hydration product, comprising performing hydration reaction of olefin in the presence of the carbon-based solid acid according to any one of the first to fourth aspects of the invention.
• a sixth aspect of the invention relates to a method for producing an ether, comprising performing etherification reaction of olefin in the presence of the carbon-based solid acid according to any one of the first to fourth aspects of the invention.
• a seventh aspect of the invention relates to a method for producing an ester, comprising performing esterification reaction by reacting acid with alcohol in the presence of the carbon-based solid acid according to any one of the first to fourth aspects of the invention.
• An eighth aspect of the invention relates to a catalyst comprising a carbon-based solid acid obtained by carbonization and sulfonation of an organic substance, which has a reduction rate of 10 mol% or less of acid content caused by immersing the solid acid in hot water of 120°C for 2 hours.
• the carbon-based solid acid according to the present invention has high thermal and chemical stabilities and hardly causes elimination of acid by hydrolysis or the like even at high temperature, high durability (long life) can be expected in various uses.
• the carbon-based solid acid of the present invention can be industrially supplied in large amounts since it can be inexpensively produced. Further, this carbon-based solid acid shows high reaction activity, when used as a catalyst in various polar reactions such as hydration and etherification of olefins, neutralization and purification step after reaction is not necessary, the catalyst can be easily separated and reused, and an intended product can be produced efficiently at low cost without the problem of corrosion of apparatus.
• the solid acid obtained by carbonization and sulfonation of an organic substance which has a reduction rate of 10 mol% or less of acid content caused by immersing the solid acid in hot water of 120°C for 2 hours, has not been obtained in the past, and is novel as solid acid.
• the carbon-based solid acid of the present invention can be obtained by carbonizing and sulfonating an organic substance, particularly, a carbohydrate.
• an organic substance saccharides having ⁇ 1-4 glycosidic bond, specifically, polysaccharides such as cellobiose and cellulose by condensation of glucose, lignin, and amylose by condensation of glucose as saccharides having ⁇ 1-4 glycosidic bond are preferably used.
• a polysaccharide having ⁇ 1-4 glycosidic bond specifically, cellulose; lignin; and a polysaccharide having ⁇ 1-4 glycosidic bond, specifically amylose.
• Such organic substances are preferred to have a molecular weight of 1000 or more from the viewpoint of preparation of the carbon-based solid acid, since sulfuric acid is hardly diluted due to minimized generation of moisture in the carbonization and sulfonation, and the acid content is thus improved.
• These saccharides can be used independently or in combination of two or more kinds thereof, and further can be used in combination with other organic substances within the limit of not impairing the effect of the invention. In such a case, it is preferred that the above-mentioned saccharides are principally contained (50% or more).
• a carbon-based solid acid having a reduction rate of 10 mol% or less of acid content caused by immersing the solid acid in hot water of 120°C for 2 hours can be obtained.
• the carbonization of the organic substance mentioned above is attained by performing heat treatment under an inert gas atmosphere of nitrogen or the like, and an amorphous black solid (carbonized material) is obtained thereby.
• the sulfonation is attained by performing heat treatment in concentrated sulfuric acid or fuming sulfuric acid, whereby sulfonic acid group is added to the skeleton of the carbonized material.
• the sulfonation is preferably performed after completion of the carbonization, but may be performed simultaneously with the carbonization.
• the conditions for the carbonization and the sulfonation are properly selected depending on the kind of the organic substance to be used.
• the carbonization is preferably performed in nitrogen atmosphere at 250 to 600°C for 1 to 50 hours, and the sulfonation is preferably performed at 100 to 450°C for 0.5 to 30 hours.
• the degree of carbonization is determined based on the degree of graphitization, and the peak intensity ratio D/G of D-peak to G-peak in Raman spectroscopy that is one of indexes (parameters) showing the degree of graphitization is 0.5 or more.
• the graphitization is not performed to 100%.
• the heating temperature in simultaneous treatment of carbonization and sulfonation is preferably 100 to 300°C, further preferably 150 to 270°C.
• removal of excessive sulfuric acid is performed by washing with hot water, and drying is further performed, whereby the carbon-based solid acid of the invention can be obtained.
• the washing with hot water can be easily performed, for example, under reflux at about 100°C by means of Soxhlet extraction or the like.
• the washing time can be also shortened by performing the washing at high temperature under pressure.
• the washing with hot water is performed until sulfuric acid in washing water becomes substantially undetectable.
• the carbon-based solid acid of the invention is substantially amorphous such that any structure cannot be confirmed from an X-ray diffraction pattern.
• the thus-obtained carbon-based solid acid of the invention has high thermal stability with the reduction rate of acid content being as small as 10 mol% or less in a hot water heat resistance evaluation test performed by immersing the solid acid in hot water of 120°C for 2 hours.
• the measurement of reduction in acid content is performed to the carbon-based solid acid before and after the hot water treatment by conventionally known neutralization titration method, back titration method or the like.
• the carbon-based solid acid of the present invention can be industrially used as catalyst advantageously in various reactions, for example, in polar reaction, since the reduction rate of acid content during the reactions is low.
• the carbon-based solid acid of the invention has such acid strength and acid content as to be useful for acid catalysis as solid acid catalyst.
• This solid acid is advantageously used, preferably, as catalyst for various polar reactions such as esterification reaction of alcohol with acid, and hydration reaction and etherification reaction of olefins, although it can function as an acid catalyst even under a hydrophobic condition.
• this solid acid is useful as catalyst for a polar reaction using a polar substance such as alcohol, carboxylic acid or water as a reactive substrate, since it exhibits excellent durability in such a polar reaction.
• Olefin hydration reaction of olefins with water
• olefin etherification reaction of olefins with alcohol
• olefin esterification reaction of carboxylic acid with alcohol
• olefins used in the present invention there is no particular limit on the olefins used in the present invention, and straight, branched and cyclic ones can be used. However, olefins having a carbon number of 2 to 5, specifically, propylene, and butenes such as 1-butene, 2-butene and isobutene are preferably used.
• the water to be used in the hydration is not particularly limited, it is preferred to use ion-exchange water or distilled water (including vapor condensate).
• the alcohols used for the etherification reaction are not particularly limited. However, alcohols having a carbon number of 1 to 4, specifically, methanol, ethanol, and isopropyl alcohol are preferably used.
• the molar ratio of water or alcohol to olefin is set generally to 0.1 to 10, preferably to 0.3 to 7, further preferably to 1 to 5 although it is not particularly limited. If the amount of water or alcohol is too small, a side reaction such as dimerization of olefin is caused, and if it is too large, the productivity is undesirably deteriorated.
• the same alcohols as those described above can be used.
• the carboxylic acid used for the esterification include saturated or unsaturated carboxylic acids having a carbon number of 1 to 4, specifically, acetic acid, acrylic acid, and methacrylic acid.
• the molar ratio of the alcohol to the acid is set generally to 0.1 to 100 although it is not particularly limited thereto.
• the acid to be used may be anhydride.
• the reaction temperature in the hydration reaction and etherification reaction of olefins is set generally to 60°C or higher for promoting the reaction, and preferably to 100°C or higher, further preferably to 120°C or higher for ensuring high activity.
• the reaction temperature is set preferably to 250°C or lower, since an excessively high temperature may cause decomposition of the catalyst.
• the reaction pressure is set generally to 1 MPa or more, for promoting the reaction, preferably to 3 MPa or more, further preferably to 5 MPa or more although it is not particularly limited thereto.
• the reaction pressure is set preferably to 20 MPa or less since an excessively high pressure may lead to increase in facility cost. It can be properly selected depending on the reaction form.
• any one of gas phase, liquid phase and gas-liquid mixed phase can be adapted.
• a temperature of 100°C or lower is usually adapted.
• the etherification reaction is usually performed at 80 to 100°C, and the hydration reaction (isobutene) is performed at 60 to 100°C.
• the same condition can be adapted also in the esterification.
• the reaction can be easily promoted by appropriately removing water generated in accordance with the progress of the reaction from the reaction system.
• a solvent can be used together.
• an amphipathic solvent is preferred for preventing separation of the reaction solution to water phase and oil phase.
• ethers, glycol ethers, alcohols, ketones and the like can be used.
• the solvent is usable similarly in the etherification reaction, the solvent is not needed unless phase separation occurs.
• the hydration reaction of olefins in the present invention is simpler in process than an indirect hydration method using sulfuric acid catalyst (two-stage reaction of sulfuric acid esterification and hydrolysis) since it is a direct hydration method (single stage reaction).
• the indirect hydration method needs a neutralization and purification step for removal of sulfuric acid, a concentration step for reuse of sulfuric acid and like steps, which complicate the process.
• the catalyst can be easily separated for reuse by filtration, centrifugal separation or the like since the catalyst is solid, and the neutralization and purification step as in the indirect hydration method is not needed since the reaction solution after removing the catalyst contains no acid catalyst component. Reaction products can be appropriately purified by distillation or the like after the catalyst removal. Reactive distillation can be also performed.
• reactive distillation or a method by fixed bed is generally adapted.
• the carbon-based solid acid A was subjected to X-ray analysis.
• X-ray analysis an X-ray refraction device (MXP 18VAHF) by Mac Science Co., Ltd. was used for measurement.
• MXP 18VAHF X-ray refraction device
• this solid acid was found to be an amorphous substance.
• the carbon-based solid acid A was then subjected to elemental analysis.
• elementar vario EL was used for measurement. As a result, it was found that sulfonic acid group was introduced to this solid acid with inclusion of sulfur in a C/S ratio of 74.7.
• the carbon-based solid acid A was subjected to 13C-DDMAS nuclear magnetic resonance spectral analysis.
• NMR Systems 400WB by Varian Inc. was used for measurement.
• the carbons of the solid acid were mostly derived from aromatic group.
• the degree of graphitization of the carbon-based solid acid A was measured. Raman spectroscopic analysis was used for the measurement.
• Each of various alcohols was put in a 200-cc autoclave with stirrer in a predetermined amount, 0.20 g of the carbon-based solid acid A was added thereto followed by sealing, and each of various olefins was injected and sealed therein in a predetermined amount.
• the reaction mixture was heated to a predetermined temperature while stirring at 700 rpm, pressure-adjusted with nitrogen as needed, and then retained at the predetermined temperature to thereby perform etherification reaction for 2 hours. After completion of the reaction, the reaction mixture was cooled and then subjected to quantitative analysis by TCD-GC.
• the measurement of acid content of the catalyst was performed by back titration, and the measured acid content was compared with the acid content before the reaction to measure the reduction rate of the acid content.
• a solid acid was prepared according to Example 1, except that lignin was used as the raw material instead of cellulose. As a result, 24.8 g of carbonized material was recovered after the heat treatment, and 3 g of the carbonized material was sulfonated to thereby obtain 3.20 g of a carbon-based solid acid B. The acid content of the solid acid measured by back titration was 3.57 mmol/g.
• Hot water heat resistance evaluation test was performed to the carbon-based solid acid B by the same method as in Example 1. As a result, the acid content after testing was 3.51 mmol/g, with the reduction rate of acid content being 2 mol%.
• a solid acid was prepared according to Example 1, except that amylose was used as the raw material instead of cellulose. As a result, 18 g of carbonized material was recovered after the heat treatment, and 3 g of the carbonized material was sulfonated to thereby obtain 1.20 g of a carbon-based solid acid C. The acid content of the solid acid measured by back titration was 3.33 mmol/g.
• Hot water heat resistance evaluation test was performed to the carbon-based solid acid C by the same method as in Example 1. As a result, the acid content after testing was 3.28 mmol/g, with the reduction rate of acid content being 2 mol%.
• a solid acid was prepared according to Example 1, except that glucose was used as the raw material instead of cellulose. As a result, 11.7 g of carbonized material was recovered after the heat treatment, and 3 g of the carbonized material was sulfonated to thereby obtain 3.12 g of a carbon-based solid acid E. The acid content of the solid acid measured by back titration was 3.05 mmol/g.
• Hot water heat resistance evaluation test was performed to the carbon-based solid acid E by the same method as in Example 1.
• the acid content after testing was 2.41 mmol/g, with the reduction rate of acid content being 21 mol%.
• the reduction rates of acid content after testing as measured by changing the evaluation test temperature to 180°C and 210°C were 28 mol% and 33 mol%, respectively, which are apparently inferior in heat resistance to those of the solid acids of Examples of present invention.
• the carbon-based solid acid E was subjected to hydration reaction by the same method as in Example 1.
• the reaction conditions and reaction results are summarized in Table 4-1.
• the reduction rate of acid content in each reaction is large, compared with those of Examples, which shows that the heat resistance is low.
• the carbon-based solid acid E was subjected to etherification reaction by the same method as in Example 1.
• the reaction conditions and reaction results are shown in Table 4-2.
• the reduction rate of acid content in each reaction is large, compared with those of Examples, which shows that the heat resistance is low.
• the carbon-based solid acid F was subjected to hot water heat resistance evaluation test by the same method as in Example 1.
• the acid content after testing was 2.71 mmol/g, with the reduction rate of acid content being 20 mol%, which is significantly inferior in heat resistance to those of the solid acids of Examples of present invention.
• the carbon-based solid acid F was subjected to hydration reaction by the same method as in Example 1.
• the reaction condition and reaction result are shown in Table 6.
• the reduction amount of acid content in this reaction is large, compared with those in Examples, which shows that the heat resistance is low.
• the solid acid of the present invention has high thermal stability and a low reduction rate of acid content even under high temperature in actual reactions, and is suitable for industrial long-term operations.
• the solid acid of the present invention is suitable for industrial long-term operations due to the high thermal stability and minimized reduction in acid content under high temperature.
• this solid acid can be used as acid catalyst for reactions such as hydration of olefins, etherification of olefins, and esterification by reaction of acid with alcohol.

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